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Publication numberUS4629685 A
Publication typeGrant
Application numberUS 06/795,591
Publication dateDec 16, 1986
Filing dateNov 6, 1985
Priority dateNov 16, 1984
Fee statusPaid
Also published asCA1258946A, CA1258946A1, DE3580655D1, EP0182745A2, EP0182745A3, EP0182745B1, US4677186, US4808732
Publication number06795591, 795591, US 4629685 A, US 4629685A, US-A-4629685, US4629685 A, US4629685A
InventorsJosef Pfeifer
Original AssigneeCiba-Geigy Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for irradiating polyimides
US 4629685 A
Abstract
Homopolyimides and copolyimides which contain structural elements of the formula I ##STR1## in which R1 and R2 are halogen, nitro, aryl, aryloxy, alkyl or alkoxy, m is 0 or a number from 1 to 4, n is 0 or a number from 1 to 3 and p is 0, 1 or 2, the free carbonyl groups are bonded in the ortho-position relative to one another and R is a divalent aromatic radical which is substituted by at least one alkyl group or aralkyl group, are autophotocross-linkable. They are suitable for the production of protective films and photographic relief images.
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Claims(16)
What is claimed is:
1. A process for the production of a protective film or photographic relief image which comprises
irradiating a coated material, directly or through a photo-mask, said coated material being a layer of a polyimide applied to the surface of a carrier material, the polyimide being a homopolyimide or copolyimide which contains structural elements of aromatic aminodicarboxylic acids and has an intrinsic viscosity of at least 0.1 dl/g, measured at 25 C. in a solution of 0.5% by weight of polyimide in N-methylpyrrolidone, which contains recurring structural elements of the formula I ##STR43## in which R1 and R2 are halogen, nitro, aryl, aryloxy, alkyl or alkoxy, m is 0 or a number from 1 to 4, n is 0 or a number from 1 to 3 and p is 0, 1 or 2, the free carbonyl groups are bonded in the ortho-position relative to one another and R is a divalent aromatic radical which is substituted by at least one alkyl group or aralkyl group, and
developing the material.
2. A process according to claim 1 where in the polyimide of formula I; m, n and p are 0.
3. A process according to claim 1 where in the polyimide of formula I the carbonyl groups are bonded in the 2-, 3- and 6-positions.
4. A process according to claim 1 where in the polyimide of formula I the aromatic radical R is substituted by an alkyl or aralkyl group in at least one ortho-position relative to the N-atom.
5. A process according to claim 1 where in the polyimide of formula I the divalent aromatic R is substituted by benzyl or C1 -C12 -alkyl.
6. A process according to claim 5 wherein the divalent aromatic radical R is substituted by C1 -C12 -alkyl.
7. A process according to claim 6 wherein the alkyl is methyl, ethyl or isopropyl.
8. A process according to claim 1 where in the polyimide of formula I the aromatic radical R is a phenylene or bisphenylene radical substituted by alkyl.
9. A process according to claim 8 wherein the radical R has the formula II ##STR44## in which q is 0 or 1, R3 is a direct bond or a bridge group, R4 is alkyl with 1 to 4 C atoms and R5 and R11 are hydrogen atoms or alkyl with 1 to 4 C atoms, and the free bonds are in the meta- or para-position relative to the R3 group.
10. A process according to claim 9 wherein R3 is a direct bond or, as a bridge member, --S--, --SO--, --SO2 --,--CO--, --CH2 --, --O-- or C2 -C6 -alkylidene.
11. A process according to claim 1 where the polyimide contains structural elements of the formula ##STR45##
12. A process according to claim 1 wherein the polyimide contains
(a) 0.1-100 mol % of structural elements of the formula I and
(b) 99.9-0 mol % of structural elements of the formula III and/or IIIa ##STR46## in which Z is the tetravalent radical of an aromatic tetracarboxylic acid onto which in each case two carbonyl groups are bonded in the ortho- or peri-position, Z' is the trivalent radical of an aromatic aminocarboxylic acid onto which two carbonyl groups are bonded in the ortho- or peri-position and X is the divalent radical of an organic diamine.
13. A process according to claim 12 where in the structural elements of formula III, Z has the formula ##STR47## in which the free bonds are in the ortho-position relative to one another.
14. A process according to claim 12 where in the structural elements of formula III, X is a divalent phenylene or bisphenylene radical which is substituted by C1 -C12 -alkyl in at least one ortho-position relative to at least one N atom.
15. A process according to claim 12 where in the structural elements of formula IIIa, Z' is a radical of the formula ##STR48## in which R12 is a bridge group or a direct bond, two free bonds being in the ortho-position relative to one another.
16. A process according to claim 12 where in the structural elements of formula III, X is alkylene, cycloalkylene, aralkylene or arylene.
Description

The present invention relates to homopolyimides and copolyimides of substituted aromatic aminodicarboxylic acids, aromatic tetracarboxylic acids and diamines and/or unsubstituted aromatic aminodicarboxylic acids, a process for their preparation and their use for the preparation of protective films or photographic relief images.

Polyimides are plastics with useful thermomechanical properties. Because of their high melting ranges, however, they cannot be processed by the usual shaping methods for thermoplastics. Soluble polyimides which can be used as varnishes for forming coating layers with a high stability towards heat have therefore been developed, c.f. German Auslegeschrift No. 1,962,588 and U.S. Pat. No. 3,787,367. With the development of electronics and semiconductor technology, high requirements are being imposed on the heat stability of polyimides, for example as insulating and protective films, which the known polyimides are not always capable of meeting.

It has now been found that soluble autophotocrosslinkable polyimides of high heat stability are obtained if they contain structural elements of an aromatic aminoketodicarboxylic acid substituted by alkyl or aralkyl.

The present invention relates to homopolyimides and copolyimides which contain structural elements of aromatic aminodicarboxylic acids and have an intrinsic viscosity of at least 0.1 dl/g, measured at 25 C. in a solution of 0.5 percent by weight of polyimide in N-methylpyrrolidone, which contain recurring structural elements of the formula I ##STR2## in which R1 and R2 are halogen, nitro, aryl, aryloxy, alkyl or alkoxy, m is 0 or a number from 1 to 4, n is 0 or a number from 1 to 3 and p is 0, 1 and 2, the free carbonyl groups are bonded in the ortho-position relative to one another and R is a divalent aromatic radical which is substituted by at least one alkyl group or aralkyl group.

The intrinsic viscosity is preferably at least 0.2 dl/g, in particular 0.2 to 2.0 dl/g. In formula I, m, n and p are preferably 0.

R1 and R2 as halogen are preferably F or Cl, as aryl are phenyl, as aryloxy are phenoxy and as alkyl and alkoxy preferably contain 1 to 12, in particular 1 to 4, C atoms. Examples are methyl, ethyl, n-propyl, i-propyl, butyl, methoxy and ethoxy. The carbonyl groups are preferably bonded in the 2-, 3- and 6-position.

The aromatic radical R is preferably substituted by alkyl or aralkyl in at least one, in particular in both, ortho-positions relative to the N atom. The substituent as aralkyl is, in particular, benzyl. As alkyl, the substituent preferably contains 1 to 12, in particular 1 to 4, C atoms. The alkyl can be linear or branched. Ethyl, methyl, and isopropyl are particularly preferred. Other examples are n-propyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl and dodecyl.

The aromatic radical R is preferably a phenylene radical or bisphenylene radical substituted by alkyl. In particular, the radical R has the formula II ##STR3## in which q is 0 or 1, R3 is a direct bond or a bridge group, R4 is alkyl with 1 to 4 C atoms and R5 to R11 are hydrogen atoms or alkyl with 1 to 4 C atoms, and the free bonds are in the meta- or para-position relative to the R3 group.

In one embodiment, R4 and R5, and R10 and R11 are bonded in the ortho-position relative to the free bond and are C1 -C4 -alkyl. In a particularly preferred embodiment, q in formula II is 0 and R4 to R7 are C1 -C4 -alkyl, in particular methyl or ethyl.

The bridge group R3 can have the same meaning as R13. R3 is preferably a direct bond, --S--, --O--, --SO--, --SO2 --, --CO--, --CH2 -- or C2 -C6 -alkylidene, for example ethylidene, 1,1- or 2,2-propylidene, butylidene, cyclopentylidene or cyclohexylidene.

In a particular embodiment, the polyimides according to the invention contain structural elements of the formula ##STR4##

In another embodiment, the polyimides contain

(a) 0.1-100 mol % of structural elements of the formula I and

(b) 99.9-0 mol % of structural elements of the formula III and/or IIIa ##STR5## in which Z is the tetravalent radical of an aromatic tetracarboxylic acid onto which in each case two carbonyl groups are bonded in the ortho- or peri-position, Z' is the trivalent radical of an aromatic aminocarboxylic acid onto which two carbonyl groups are bonded in the ortho- or peri-position and X is the divalent radical of an organic diamine.

The structural elements of the formula I are preferably present in an amount of 5-100 mol %, preferably 20-100 mol %, in particular 50-100 mol % and especially 80-100 mol %, and the structural elements of the formulae III or IIIa are preferably present in an amount of 95-0 mol %, preferably 80 to 0 mol %, in particular 50 to 0 mol % and especially 20 to 0 mol %.

X in formula III can be a divalent unsubstituted or substituted aliphatic radical, which can be interrupted by heteroatoms or aromatic, heterocyclic or cycloaliphatic groups, an unsubstituted or substituted heterocyclic, cycloaliphatic or araliphatic radical, an aromatic radical in which two aryl nuclei are linked via an aliphatic group, or an aromatic radical which is substituted by at least one alkyl group, cycloalkyl group, alkoxyalkyl group, alkoxy group, alkylthio group, alkylthioalkyl group, hydroxyalkyl group, hydroxyalkyl group, hydroxyalkylthio group or aralkylthio group or, on two adjacent C atoms of the aromatic radical, by an alkylene group.

X is preferably alkylene, cycloalkylene, aralkylene or arylene, and especially substituted arylene.

X in formula III as a divalent aliphatic radical preferably contains 2 to 30, in particular 6 to 30 and especially 6 to 20, C atoms. In a preferred sub-group, X is linear or branched alkylene, which can be interrupted by oxygen atoms, S, SO, SO2, NH, NRa, .sup.⊕ NR2 a G.sup.⊖, cyclohexylene, naphthylene, phenylene or hydantoin radicals. Ra can be, for example, alkyl with 1 to 12 C atoms or cycloalkyl with 5 or 6 ring C atoms, phenyl or benzyl. G.sup.⊖ is an anion of a proton acid, for example halide, sulfate or phosphate. In a preferred embodiment, R and R' are linear or branched alkylene with 6 to 30 C atoms, --(CH2)m' --R14 --(CH2)n' --, in which R14 is phenylene, naphthylene, cyclopentylene or cyclohexylene and m' and n' independently of one another are the number 1, 2 or 3, --R15 --(OR16)p --O--R15 --, in which R15 is ethylene, 1,2-propylene, 1,3-propylene or 2-methyl-1,3-propylene and R16 is ethylene, 1,2-propylene, 1,2-butylene, 1,3-propylene or 1,4-butylene and p is a number from 1 to 100, or ##STR6##

Examples of aliphatic radicals are: methylene, ethylene, 1,2- or 1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,3- or 1,5-pentylene, hexylenes, heptylenes, octylenes, decylenes, dodecylenes, tetradecylenes, hexadecylenes, octadecylenes, eicosylenes, 2,4,4-trimethylhexylene, 1,10-dialkyldecylene, in which the alkyl preferably contains 1 to 6 C atoms, substituted 1,11-undecylenes, such as are described, for example, in B-0,011,559, jeffamines, for example ##STR7## where p'=1 to 100, or

--(CH2)3 (O(CH2)4)p' O--CH2,

where p'=1-100, dimethylenecyclohexane, xylylene and diethylbenzene. X is particularly preferably longer-chain, branched alkylene with, for example, 8 to 30 C atoms.

X in formula I as an aliphatic radical can also be a polysiloxane radical of the formula ##STR8## in which R18 and R17 are C1 -C6 -alkyl, in particular methyl, or phenyl, R19 is cycloalkylene, for example cyclohexylene, and in particular C1 -C12 -, especially C1 -C6 -alkylene, for example 1,3-propylene or 1,4-butylene, and x is a rational number of at least 1, for example 1 to 100, preferably 1 to 10. Such diamines containing this radical are described in U.S. Pat. No. 3,435,002 and U.S. Pat. No. 4,030,948.

The aliphatic radicals interrupted by heterocyclic radicals can be, for example, those which are derived from N,N'-aminoalkylated hydantoins or benzimidazoles. Examples are N,N'-(γ-aminopropyl)-5,5-dimethyl-hydantoin or -benzimidazolone and those of the formula ##STR9## in which Rb is alkylene with 1 to 12, preferably 1 to 4, C atoms, or ##STR10## in which Rc is a hydrogen atom or methyl and a is an integer from 1 to 20.

Examples of suitable substituents for the aliphatic radicals are hydroxyl, halide, such as F or Cl, and alkoxy with 1 to 6 C atoms.

Heterocyclic diamine radicals are preferably derived from N-heterocyclic diamines, for example from pyrrolidine, indole, piperidine, pyridine and pyrrole, the N atom of which can be alkylated, for example methylated. An example is N-methyl-4-amino-5-aminomethylpiperidine.

X in formula I as a divalent cycloaliphatic radical preferably contains 5 to 8 ring C atoms and is, in particular, mononuclear or dinuclear cycloalkylene which has 5 to 7 ring C atoms and is unsubstituted or substituted by alkyl, which preferably contains 1 to 4 C atoms. In a preferred embodiment, X as a cycloaliphatic radical is a radical of the formula ##STR11## in which q' is 0 or 1, the radicals R20 independently of one another are hydrogen or alkyl with 1 to 6 C atoms and X' is a direct bond, O, S, SO2, alkylene with 1 to 3 C atoms or alkylidene with 2 to 6 C atoms. R20 is preferably ethyl or methyl, X' is preferably methylene and the alkylidene preferably contains 2 or 3 C atoms, such as ethylidene and 1,1- or 2,2-propylidene.

Examples of X as cycloalkylene are: 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1,4-cyclohexylene, cycloheptylene, cyclooctylene, methylcyclopentylene, methyl- or dimethylcyclohexylene, 3- or 4-methylcyclohex-1-yl, 5-methyl-3-methylenecyclohex-1-yl, 3,3'- or 4,4'-bis-cyclohexylene, 3,3'-dimethyl-4,4'-biscyclohexylene, 4,4'-biscyclohexylene ether or sulfone or -methane or -2,2-propane and the radicals of bis-aminomethyl-tricyclodecane, bis-aminomethylnorbornane and menthanediamine.

X as a cycloaliphatic radical is particularly preferably 1,4- or 1,3-cyclohexylene, 2,2,6-trimethyl-6-methylenecyclohex-4-yl, methylbenebis(cyclohex-4-yl) or methylenebis(3-methylcyclohex-4-yl).

X as an araliphatic radical preferably contains 7 to 30 C atoms. If the aromatic group of the araliphatic radical is bonded to the N atoms in the radical of the formula III, which is preferred, these aromatic groups are preferably substituted in the same way as X as an aromatic radical, including the preferred substitution. The araliphatic radical preferably contains 7 to 30, in particular 8 to 22, C atoms. The aromatic radical in the araliphatic radical is preferably a phenyl radical. X as an araliphatic radical is, in particular, aralkylene which is unsubstituted or substituted on the aryl by alkyl, the alkylene radical being linear or branched. In a preferred embodiment, the araliphatic radical has the formula ##STR12## in which the radicals R20 independently of one another are hydrogen atoms or, in particular, alkyl with 1-6 C atoms and the symbols r are integers from 1 to 20.

The free bond can be in the o-position, m-position and, in particular, in the p-position relative to the Cr H2r group, and one or both radicals R20 are preferably bonded in the o-position relative to the free bond.

Examples of X as an araliphatic radical are: m- or p-benzylene, 3-methyl-p-benzylene, 3-ethyl-p-benzylene, 3,5-dimethyl-p-benzylene, 3,5-diethyl-p-benzylene, 3-methyl-5-ethyl-p-benzylene, p-phenylenepropylene, 3-methyl-p-phenylenepropylene, p-phenylenebutylene, 3-ethyl-p-phenylenepentylene and, in particular, longer-chain phenylenealkylene radicals, which are described, for example, in A-0,069,062: 6-(p-phenylene)-6-methylhept-2-yl, 6-(3'-methyl-p-phenylene)-6-methylhept-2-yl, 6-(3'-ethyl-p-phenylene)-6-methylhept-2-yl, 6-(3', 5'-dimethyl-p-phenylene)-6-methylhept-2-yl, 11-(p-phenylene)-2,11-dimethyl-dodec-1-yl and 13-(p-phenylene)-2,12-dimethyltetradec-3-yl.

X can also be an aromatic radical in which two aryl nuclei, in particular phenyl, are linked via an aliphatic group. This radical preferably has the formula ##STR13## in which the free bonds are in p-, m- and, in particular, o-position relative to the Q' group and Q' is C1 -C12 -, in particular C1 -C6 -alkylene, which can be interrupted by O or S. Examples of Q' are ethylene, 1,2- or 1,3-propylene, butylene, --CH2 --O--CH2, --CH2 --S--CH2 -- and --CH2 CH2 --O--CH2 CH2.

Particularly preferred copolyimides are those with structural elements of the formula III in which X is substituted aromatic radicals. The substituent on the aromatic radical preferably contains 1 to 20, in particular 1-12 and especially 1-6 C atoms. The substituent is, in particular, C5 - or C6 -cycloalkyl, linear or branched alkyl, alkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl, hydroxyalkyl, hydroxyalkoxy or hydroxyalkylthio with 1 to 6 C atoms, benzyl, trimethylene or tetramethylene. The preferred alkoxyalkyl is alkoxymethyl and the preferred alkoxy is methoxy. Examples of the substituents are: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, tetradecyl, eicosyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, butoxymethyl, benzyl, methylbenzyl, phenylethyl, methylthio, ethylthio, hydroxyethyl, methylthioethyl and hydroxyethylthio. Preferred radicals are methoxymethyl, ethoxymethyl, methyl, ethyl, n-propyl, i-propyl, trimethylene and tetramethylene, cyclopentyl and cyclohexyl. Methyl, ethyl and i-propyl are particularly preferred. The substituted aromatic radical can be a mononuclear or polynuclear, in particular dinuclear, radical. Mononuclear radicals can contain 1 to 4, preferably 1 or 2, substituents and dinuclear radicals can contain up to 4, preferably 1 or 2, substituents in each nucleus. It has been found that copolyimides have a high photosensitivity if one or two substituents are bonded in the ortho-position relative to the N atom. Substitution in the ortho-position is therefore preferred. The aromatic radical is preferably bonded in the meta- or para-position relative to the N atom.

X as a substituted aromatic radical can contain 7 to 30, in particular 7 to 20, C atoms. The aromatic radical is preferably a hydrocarbon radical, for example phenylene, naphthylene or bisphenylenes, or a pyridine radical, these being substituted as defined above.

A preferred sub-group are those aromatic radicals of the formulae ##STR14## in which R20, in the case of monosubstitution, is alkyl with 1 to 6 C atoms and the other radicals R20 are hydrogen, and in the case of di-, tri- or tetra-substitution, two radicals R20 are alkyl with 1 to 6 C atoms and the other radicals R20 are hydrogen atoms or alkyl with 1 to 6 C atoms, or in the case of di-, tri- or tetra-substitution, two vicinal radicals R20 in the phenyl ring are trimethylene or tetramethylene and the other radicals R20 are hydrogen atoms or alkyl with 1 to b 6 C atoms, Y" is O, S, NH, CO or CH2, R21 is a hydrogen atom or alkyl with 1 to 5 C atoms and R22 is alkyl with 1 to 5 C atoms, and Z" is a direct bond, O, S, SO, SO2, ##STR15## NR23, CONH, NH, R23 SiR24, R23 OSiOR24, ##STR16## alkylene with 1 to 6 C atoms, which can be interrupted by --O-- or --S--, alkenylene or alkylidene with 2 to 6 C atoms, phenylene or phenyldioxyl, in which R23 and R24 independently of one another are alkyl with 1 to 6 C atoms or phenyl and j is 1-10, in particular 1-3. Z" can furthermore have the formula ##STR17## in which G is S or, in particular, 0, f is 0 or, in particular, 1, g is 1-6 and h is 1 to 50, in particular 1 to 10, and R18 and R17 are as defined above, or can be a radical of the formula ##STR18## in which K is ##STR19## where R25 is H, C1 -C6 -alkyl or phenyl. R21 and R22 are preferably methyl, Y" is preferably --CH2 -- or --O-- and Z" is preferably a direct bond, --O--, --CH2 -- or alkylidene with 2 to 4 C atoms. R23 and R24 are, in particular, methyl, ethyl and phenyl. The alkylene preferably contains 2 to 4 C atoms and is, in particular, ethylene, Alkenylene is, in particular, ethenylene.

A preferred sub-group are toluylene radicals and radicals of o,o'-substituted and diaminodiphenylenes, diaminodiphenylmethanes and diaminodiphenyl ethers.

A particularly preferred group are those aromatic radicals of the formulae ##STR20## in which Z"' is a direct bond, 0 or, in particular, CH2 and R26 is a hydrogen atom, methyl, ethyl or isopropyl.

Examples of substituted aromatic radicals X are: 4-methyl-1,3-phenylene, 4-ethyl-1,3-phenylene, 2-methyl-1,3-phenylene, 4-benzyl-1,3-phenylene, 4-methoxymethyl-1,3-phenylene, tetrahydro-1,3- or -1,4-naphthylene, 3-propyl-1,3- or -1,4-phenylene, 3-isopropyl-1,4-phenylene, 3,5-dimethyl-1,4-phenylene, 2,4-dimethyl-1,3-phenylene, 2,3-dimethyl-1,4-phenylene, 5-methyl-1,3-phenylene, 2,3,5,6-tetramethyl-1,4- or -1,3-phenylene, 3-methyl-2,6-pyridylene, 3,5-dimethyl-2,6-pyridylene, 3-ethyl-2,6-pyridylene, 1-methyl-2,7-naphthylene, 1,6-dimethyl-2,7-naphthylene, ##STR21## in which A, B, C, D and E are as defined in the following table. The free positions in the phenyl nuclei here can be occupied by one or two other substituents G or H in each nucleus, and G or H can have the meaning of A to D given in the following table:

______________________________________E            A        B        C      D______________________________________CH2     Methyl   Methyl   H      HCH2     Methyl   Ethyl    H      HCH2     Ethyl    Ethyl    H      HCH2     Isopropyl                 Isopropyl                          H      HCH2     Methoxymethyl H        HCH2     Benzyl   Benzyl   H      HCH2     Methyl   Methyl   Methyl HCH2     Ethyl    Ethyl    Ethyl  HCH2     Isopropyl                 Isopropyl                          Methyl MethylCH2     Methoxymethyl Methyl   HCH2     Methyl   Ethyl    Methyl HCH2     Methoxymethyl MethoxymethylCH2     Methyl   Methyl   Methyl MethylCH2     Ethyl    Ethyl    Ethyl  EthylCH2     Methyl   Methyl   Ethyl  EthylCH2     Ethyl    Ethyl    Isopropyl                                 IsopropylCH2     Isopropyl                 Isopropyl                          Isopropyl                                 IsopropylCH2     Isopropyl                 Isopropyl                          Methyl HCH2     Methoxy  Methoxy  Methyl MethylO            Methyl   Methyl   H      HO            Ethyl    Ethyl    H      HO            Methyl   Methyl   Methyl HO            Methyl   Methyl   Methyl MethylO            Methyl   Methyl   Ethyl  EthylS            Methyl   Methyl   H      HS            Ethyl    Ethyl    H      HS            Methyl   Methyl   H      HS            Methyl   Methyl   Methyl MethylS            Ethyl    Ethyl    Ethyl  EthylS            Methyl   Methyl   Ethyl  EthylCO           Methyl   Methyl   Methyl HCO           Methyl   Methyl   H      HCO           Methyl   Methyl   Methyl MethylSO2     Methyl   Methyl   Ethyl  HSO2     Methyl   Methyl   H      HSO2     Methyl   Methyl   Methyl MethylSO2     Ethyl    Ethyl    Methyl MethylSO           Methyl   Methyl   Methyl MethylSO           Methyl   Methyl   H      HCOO          Methyl   Methyl   H      HCOO          Methyl   Methyl   Methyl MethylCONCH3  Methyl   Methyl   H      HNCH3    Methyl   Methyl   Ethyl  EthylNCH3    Methyl   Methyl   Methyl MethylCONH         Methyl   Methyl   --     --NH           Ethyl    Methyl   Ethyl  MethylNH           Methyl   Methyl   Methyl MethylSi(Methyl)2        Methyl   Methyl   H      HSi(Phenyl)2        Methyl   Methyl   Methyl MethylSi(OMethyl)2        Ethyl    Ethyl    H      HSi(OPhenyl)2        Methyl   Methyl   Methyl MethylOSi(Methyl)2 O        Methyl   Methyl   Methyl MethylEthylene     Methyl   Methyl   H      HEthylene     Methyl   Methyl   Methyl MethylEthylene     Ethyl    Ethyl    H      HEthylene     Methyl   Methyl   Ethyl  EthylPhenylene    Methyl   Methyl   Methyl MethylPhenylene    Ethyl    Ethyl    H      H ##STR22##   Methyl   Ethyl    Methyl Ethyl ##STR23##   Methyl   Methyl   Methyl Methyl ##STR24##   Methyl   Methyl   Methyl MethylDirect bond  Methyl   Methyl   H      HDirect bond  Methyl   Ethyl    Methyl EthylDirect bond  Methyl   Ethyl    Methyl HDirect bond  Ethyl    Ethyl    Ethyl  EthylDirect bond  Methoxy  Methoxy  Methoxy                                 MethoxyDirect bond  Isopropyl                 Isopropyl                          H      HDirect bond  Methoxy- Methoxy- Methoxy-                                 Methoxy-        methyl   methyl   methyl methyl______________________________________

X in formula III can also be an arylene radical which is unsubstituted or substituted by F or Cl. It can have the formula ##STR25## in which R27 is a direct bond, --O--, --S--, --SO--, --SO2 -- or --CO-- and the free bonds are in the ortho- or para-position, and q is 0 or 1. Examples are m- or p-phenylene, 3,3'- or 4,4'-bisphenylene, 3,3'- or 4,4'-bisphenylene ether or thioether or -benzophenone and 3,3'-dichlorobenzidine.

It is known that some aliphatic and aromatic diamines, for example phenylenediamine or di(aminophenyl)methane, may promote the insolubility of polyimides. Such diamines are therefore preferably employed in smaller amounts. In particular, in this case, the structural elements of the formula I are present in amounts of at least 50 mol %, in particular 80 mol % and especially 90 mol %.

Z as a tetravalent aromatic radical preferably contains 6 to 30, in particular 6 to 20, C atoms. In a preferred sub-group, Z has the formula ##STR26## in which R28 is a direct bond or a bridge group of the formula ##STR27## in which R29, R30 and R31 are alkyl with 1 to 6 C atoms, phenyl or benzyl and R30 and R31 are alkoxy with 1 to 6 C atoms, phenyloxy or benzyloxy.

In the above formulae, in each case two of the free bonds are always in the peri- and/or ortho-position.

A preferred sub-group of Z are radicals of the formulae ##STR28## in which R28 is a direct bond, --O--, --SO2 --, --CH2 -- or, in particular, --CO--.

Especially preferred radicals are those of the formulae ##STR29## or mixtures thereof. The free bonds in the benzophenone radical are in the ortho-position.

Examples of tetracarboxylic acid anhydrides with a radical Z are: 2,3,9,10-perylenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 4,4'-isopropylidenephthalic acid anhydride, 3,3'-isopropylidenediphthalic acid anhydride, 4,4'-oxydiphthalic acid anhydride, 4,4'-sulfonyldiphthalic acid anhydride, 3,3'-oxydiphthalic acid anhydride, 4,4'-methylenediphthalic acid anhydride, 4,4'-thiodiphthalic acid anhydride, 4,4'-ethylidenephthalic acid anhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-6,7-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindane-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindane-6,7-dicarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid anhydride and 4,5,3',4' -benzophenonetetracarboxylic acid anhydride.

It has furthermore been found that a higher photo-sensitivity is achieved in copolyimides if Z is the tetravalent radical of an aromatic ketotetracarboxylic acid, and especially also if X is a substituted aromatic radical as defined above. Such copolyimides are a preferred sub-group. Radicals of such ketocarboxylic acids are present, in particular, if smaller amounts of structural elements of the formula I are present. A particularly preferred radical is ##STR30## in which the free bonds are in the ortho-position relative to one another.

Other preferred radicals of ketocarboxylic acids have the formulae VIII to XI ##STR31## in which T is a direct bond, --S--, --O--, --CH2 --, --CO--, --NH--, --NR32 --, --SO--, --SO2 --, --CHR32 -- or --CR32 R33 -- and R32 and R33 are C1 -C6 -alkyl, phenyl or benzyl, and the free bonds are in the ortho-position relative to one another.

Z' in formula IIIa is preferably a radical of the formula ##STR32## in which R12 is a bridge group or a direct bond and two free bonds are in the ortho-position relative to one another. R12 as a bridge group is preferably --O--, --S--, --CO-- or --CH2 --, or alkylidene with 2 to 6 C atoms, cyclopentylidene or cyclohexylidene.

The present invention also relates to a process for the preparation of polyimides containing structural elements of the formula I according to claim 1, which comprises subjecting at least one aminodicarboxylic acid of the formula IV ##STR33## by itself or together with at least one aminodicarboxylic acid of the formula V ##STR34## and/or at least one tetracarboxylic acid of the formula VI ##STR35## or polyimide-forming derivatives thereof, and at least one diamine of the formula VII

H2 N--X--NH2                                     (VIII)

in which R, R1, R2, Z, Z', X, m, n and p are as defined above, to polycondensation and cyclisation in a manner which is known per se.

Instead of the tetracarboxylic acids and aminodicarboxylic acids, it is also possible to use their polyimide-forming derivatives, for example their esters, amides, halides, in particular the chlorides, and anhydrides.

The aminodicarboxylic acids of the formula IV are novel and the present invention also relates to them. They can be obtained, for example, in the following manner:

Mellitic acid n-butylimide is converted with SO2 Cl2 into ##STR36## and this is reacted in the presence of AlCl3 with ##STR37## to give ##STR38## This compound is nitrated with HNO3 and the nitro compound formed is hydrogenated catalytically to the desired amino compound ##STR39## The imide can be converted into its acid derivatives in a known manner.

4,4'-Ketobis-(naphthalene-1,2-dicarboxylic acid) can be obtained by reacting 2 moles of 1,2-dimethylnaphthalene with COCl2 in the presence of AlCl3 and subsequently oxidising the 4,4'-ketobis(1,2-dimethylnaphthalene) formed with HNO3 to give the tetracarboxylic acid. This tetracarboxylic acid can be partially hydrogenated to 4,4'-keto(tetrahydronaphthalene-1,2-dicarboxylic acid). The hydrogenation can also be carried out before the oxidation with 4,4'-ketobis(1,2-dimethylnaphthalene).

Tetracarboxylic acids with structural elements of the formula IV are known in some cases.

Anthraquinonetetracarboxylic acids are described, for example, in U.S. Pat. No. 3,702,318 and CA 100,1006119a (1984).

Hydrogenation of the keto groups in anthraquinonetetracarboxylic acids with, for example, NaBH4 gives the corresponding dihydroxy compound, which can be converted into anthronetetracarboxylic acid by treatment with hydrochloric acid under reflux. The CH2 group of anthronetetracarboxylic acid can be alkylated in a known manner and thus converted into the CHR32 or CR32 R33 group.

To preapare fluorenonetetracarboxylic acid, for example, 3,4-dimethyl-magnesium bromide can be dimerised in the presence of CuCl2 and the 3,3'4,4'-tetramethylbiphenyl formed can be reacted with COCl2 in the presence of AlCl3 to give tetramethylfluorenone, which can be oxidised to the tetracarboxylic acid in a known manner with, for example, HNO3.

Xanthonetetracarboxylic acid is obtained by first converting 3,3',4,4-tetramethylphenyl ether into 2,3,6,7-tetramethylxanthone with CCl4 in the presence of AlCl3 and subsequent hydrolysis with dilute HCl, and oxidising the product to the tetracarboxylic acid in the customary manner, for example with HNO3.

Tetracarboxylic acids with structural elements of the formula VIII in which T is S, SO, SO2 or NR32 can be obtained by the following route: 1-bromo-3,4-dimethylbenzene is reacted with CCl4 in the presence of AlCl3 to give bis(2-bromo-3,4-dimethylphenyl)dichloromethane.

Oxidation with 20% HNO3 gives ##STR40##

Reaction with Na2 S gives thioxanthonetetracarboxylic acid, which can be oxidised to the sulfoxide or sulfone in a known manner. Reaction with NaNH2 or R32 NH2 gives the acridonetetracarboxylic acids.

Aminodicarboxylic acids of the formula V and diamines of the formula VII, and tetracarboxylic acids of the formula VI are known, are commercially available or can be prepared by known processes. Si-containing diamines are described in U.S. Pat. Nos. 3,435,002 and A-0,054,426.

Diamines with the ##STR41## group can be prepared from the diisocyanates described in A-2,318,170. Diamines substituted by alkyl or cyclo alkyl, in particular ethyl or propyl, are accessible by alkylation of unsubstituted or partly substituted aromatic diamines with alkenes or cycloalkenes (c.f. U.S. Pat. No. 3,275,690). Polynuclear, especially dinuclear, aromatic diamines can be obtained via condensation of corresponding monoamines with aldehydes or ketones.

The polyimides according to the invention have average molecular weights (weight-average Mw) of at least 2,000, preferably at least 5,000. The upper limit depends largely on the properties which determine the processability, for example their solubility. It can be up to 500,000, preferably up to 100,000 and in particular up to 60,000. The polyimides can furthermore be random polyimides or block polyimides. They are prepared by customary processes in devices envisaged for this purpose. The reaction is advantageously carried out in solution; suitable inert solvents are listed below. The reaction temperatures can be -20 to 300 C.

Specifically, a procedure is advantageously followed in which the aminodicarboxylic acid anhydrides, tetracarboxylic acid dianhydride and diamine are first reacted to form a polyamide acid intermediate and this polyamide acid is then cyclised, water being detached. Cyclisation can be by means of heat. The cyclisation is advantageously carried out under the influence of dehydrating agents, for example carboxylic acid anhydrides, such as acetic anhydride. The polyimides can then be isolated by customary processes, for example by removal of the solvent or by precipitation by adding a nonsolvent.

Another preparation method comprises reacting the tetracarboxylic acid dianhydride with a diisocyanate in one stage to give the polyimide.

The polyimides according to the invention are soluble in various solvents, if necessary with warming, and they have high glass transition points. They are outstandingly suitable for the production of films and protective coatings, and coating agents can be used from a solution of the polyimide in a solvent. The present invention also relates to the use of the polyimides according to the invention for the production of protective coatings and films.

To produce the coated material, the polymer or mixtures thereof is advantageously dissolved in a suitable organic solvent, if necessary with warming. Examples of suitable solvents are polar, aprotic solvents, which can be used by themselves or as mixtures of at least two solvents. Examples are: ethers, such as dibutyl ether, tetrahydrofuran, dioxane, methylene glycol, dimethylethylene glycol, dimethyldiethylene glycol, diethyldiethylene glycol and dimethyltriethylene glycol, halogenated hydrocarbons, such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1,1,-trichloroethane and 1,1,2,2,-tetrachloroethane, carboxylic acid esters and lactones, such as ethyl acetate, methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, γ-butyrolactone, o-valerolactene and pivalolactone, carboxylic acid amides and lactams, such as formamide, acetamide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, γ-butyrolactam, ε-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam, tetramethylurea and hexamethylphosphoric acid amide, sulfoxides, such as dimethyl sulfoxide, sulfones, such as dimethyl sulfone, diethyl sulfone, trimethylene sulfone and tetramethylene sulfone, trimethylamine, triethylamine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine and substituted benzenes, such as chlorobenzene, nitrobenzene, phenols or cresols.

Undissolved constituents can be removed by filtration, preferably pressure filtration. The concentration of polymer in the coating agent thus obtained is preferably not more than 50% by weight, in particular not more than 30% by weight and especially not more than 20% by weight, based on the solution.

Other customary additives which do not adversely influence the photosensitivity can be incorporated during preparation of the solutions. Examples of these are matting agents, flow control agents, fine-particled fillers, flame-proofing agents, fluorescent brighteners, antioxidants, light stabilisers, stabilisers, dyes, pigments, adhesion promoters and antihalo-dyes, such as are described, for example, in U.S. Pat. No. 4,349,619.

The coating agent can be applied to suitable substrates or carrier materials by customary methods, such as dipping, brushing and spraying processes or by whirler, cascade and curtain coating. Examples of suitable substances are plastics, metals and metal alloys, semimetals, semiconductors, glass, ceramics and other inorganic materials, for example SiO2 and Si3 N4. The solvent is then removed, if necessary by warming and if necessary in vacuo. Tackfree, dry, uniform films are obtained. The films applied can have coating thicknesses of up to about 500 μm or more, preferably from 0.5 to 500 μm and especially from 1 to 50 μm, depending on the application.

Protective films of such polyimides can be further modified by the action of radiation, increased heat stabilities, for example, thereby being possible. There is also the possibility of using such polyimides as photographic recording material for relief images. Additives such as sensitisers can be avoided by direct crosslinking under the influence of radiation, and the protective coatings and images have excellent electrical properties. The protective coatings and images are furthermore distinguished by their high heat stability and by only little shrinkage, if at all, when exposed to heat, which is of considerable advantage during use because virtually no distortion of the structures reproduced is observed.

The invention also relates to a carrier material coated with such polyimides and the use of this material for the production of protective coatings and photographic relief images. The coating thickness for this application is preferably 0.5 to 100 μm, in particular 1 to 50 μm and especially 1-10 μm.

Photostructuring or photocrosslinking can be caused by high-energy radiation, for example by light, especially in the UV range, or by X-rays, laser light, electron beams and the like. The material according to the invention is outstandingly suitable for the production of protective films and passivating lacquers and as photographic recording material for heat-stable relief images.

Examples of fields of use are protective, insulating and passivating varnishes in electrical engineering and electronics, photo-masks for electronics, textile printing and the graphics industry, etch resists for the production of printed circuits and printed circuit boards and integrated switching circuits, relays for the production of X-ray masks, solder-stopping varnishes, dielectrics for multilayer circuits and structural elements for liquid crystal displays.

Protective films are produced by direct exposure, the exposure times largely depending on the coating thicknesses and the photosensitivity.

Photographic production of the relief structure is effected by image-wise exposure through a photo-mask and subsequent development, removing the non-exposed portions with a solvent or a solvent mixture, after which, if appropriate, the image produced can be stabilised by after-treatment with heat.

The invention also relates to such a process for the application of relief structures. The abovementioned solvents, for example, are suitable as developers.

The polymer coating of the material according to the invention has a photosensitivity which is sufficient for many application purposes and in some cases is high, and it can be photocrosslinked directly. The protective films and relief images are distinguished by a high adhesion and resistance to heat, mechanical stresses and chemicals. Only slight shrinkage is observed during after-treatment with heat. Additives for producing or increasing photosensitivity can furthermore be avoided. The material is stable on storage, but should advantageously be protected from the effect of light.

The following examples illustrate the invention in more detail. The glass transition temperatures are determined by differential scanning calorimetry.

(A) PREPARATION OF THE STARTING SUBSTANCES Example (a)

Preparation of ##STR42##

(1) 68.5 g of n-butylamine are added dropwise to a solution of 185 g of trimellitic anhydride in the course of 15 minutes. The mixture is then heated to the boiling point and some of the solvent is distilled off, together with the water of reaction. The solution which remains is poured into water and the product which has precipitated is filtered off and dried.

The dry product is then heated to the reflux temperature with 265 ml of thionyl chloride in the course of one hour and the mixture is kept at this temperature for a further 2 hours. When the excess thionyl chloride has been removed by distillation, the residue is recrystallised from one liter of cyclohexane. The yield of pure trimellitic acid n-butylimide-chloride (A) is 168.9 g, melting point 77-78 C.

(2) 15.5 g of Durol and 56 g of AlCl3 in 150 ml of CS2 are introduced into a flask and 28 g of A are added in portions in the course of 15 minutes. After one hour, the mixture is poured onto ice-water and 100 ml of concentrated HCl are added.

The organic layer is separated off, the aqueous layer is extracted with CH2 Cl2 and the combined organic phases are washed with water, dried over Na2 SO4 and evaporated to dryness. The residue is boiled up with 200 ml of ethanol, the mixture is filtered hot and the filtrate is cooled. 5-(2,3,5,6-Tetramethylbenzoyl)-phthalic acid n-butylimide (B) thereby precipitates as crystals. After filtering off and drying, 20.5 g of product B with a melting point of 127 C. are obtained.

Elemental analysis:

______________________________________       calculated               found______________________________________C             76.01     76.2H             6.93      7.0N             3.85      3.7O             13.21     13.2______________________________________

(3) 17 g of product B are added in portions to a mixture of 48 ml of concentrated H2 SO4 and 40 ml of 65% HNO3 at 0 to 2 C. When the addition has ended, the mixture is stirred at 0 C. for a further 2 hours, and somewhat cloudy solution is filtered and the filtrate is poured onto ice-water. The 5-(4-nitro-2,3,5,6-tetramethylbenzoyl)phthalic acid n-butylimide (C) which has precipitated is filtered off, washed with water and dried, and, without further purification, is hydrogenated in dimethylformamide with hydrogen under catalysis by Raney nickel under atmospheric pressure.

The hydrogenation product is purified over a column 50 cm long and 10 cm thick filled with silica gel 60, using toluene/ethyl acetate (80/20) as the mobile phase. 8.9 g of 5-(4-amino-2,3,5,6-tetramethylbenzoyl)phthalic acid n-butylimide (D) are obtained.

(4) To prepare the free dicarboxylic acid, compound D is refluxed with alcoholic KOH for 24 hours. During this treatment, the potassium salt precipitates gradually as the hydrolysis progresses.

The potassium salt is filtered off and dissolved in water and 2N HCl is added until the isoelectric point (pH 5-6) is reached. The 5-(4-amino-2,3,5,6-tetramethylbenzoyl)phthalic acid (E) which thereby precipitates is filtered off and dried.

Elemental analysis:

______________________________________       calculated               found______________________________________C             66.85     65.66H             5.61      5.89N             4.10      4.12O             23.44     24.01______________________________________

(5) 1 g of aminodicarboxylic acid (E) is heated at 250 C. in vacuo for 10 hours, the corresponding anhydride (F) being formed, with water being detached.

Elemental analysis:

______________________________________       calculated               found______________________________________C             70.58     70.67H             5.30      5.35N             4.33      4.49O             19.79     19.57______________________________________
EXAMPLE 1 Polycondensation of E

0.5 g of E is dissolved in 5 ml of m-cresol and the solution is kept under reflux (about 205 C.) for 4 hours. The solution is cooled and the polyimide is precipitated with alcohol. The intrinsic viscosity is 0.41 dl/g.

EXAMPLE 2

0.5 g of aminoanhydride F is dissolved in 5 ml of N-methylpyrrolidone and the solution is stirred at room temperature for 16 hours.

0.5 ml of triethylamine and 1.3 ml of acetic anhydride are then added and the mixture is stirred for a futher 24 hours.

The polymer is then precipitated by stirring into water and is dried.

Intrinsic viscosity: 0.32 dl/g

Glass transition temperature: 386 C. (differential scanning calorimetry).

EXAMPLE 3

1.642 g of 3,6-diaminodurol are dissolved in 22 ml of N-methylpyrrolidone (NMP) in a condensation vessel and 0.45 g of the aminoanhydride F is added, with stirring. After one hour, 3.22 g of benzophenonetetracarboxylic acid dianhydride (BTDA) are added. Five hours later, a further 32.2 mg of BTDA are added. After 2 hours, a mixture of 3 ml of triethylamine and 8.5 ml of acetic anhydride is added to the polyamide acid solution and stirring is continued for 20 hours. The polyimide is worked up by stirring the solution into water and filtering off and drying the product which precipitates.

Intrinsic viscosity: 1.04 dl/g

Tg: 430 C.

Application Example

A thin film is produced on a sheet of plastic, which has been laminated with copper on one side, by whirling on a 10% solution of the polymer according to Example 1 in N-methylpyrrolidone and then removing the solvent in a circulating air oven. The sheet thus coated is then exposed through a photo-mask (Stouffer wedge) at room temperature with a UV lamp (1,000 watt) from a distance of 18 cm for 360 seconds.

The exposed sheet is developed with N-methylpyrrolidone, the non-exposed portions being dissolved away. The relief image is then rendered visible by etching away the exposed copper layer with FeCl3 solution.

The photosensitivity according to the "21 step Stouffer sensitivity guide" is 4 steps.

The copolyimide according to Example 3 has a photosensitivity of 7-8 steps using the same method with an exposure time of 20 seconds.

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US4694061 *Oct 4, 1984Sep 15, 1987Ciba-Geigy CorporationRadiation-sensitive polycondensates, processes for their preparation coated material and its use
US4786569 *Aug 27, 1986Nov 22, 1988Ciba-Geigy CorporationAdhesively bonded photostructurable polyimide film
US4838900 *Apr 13, 1988Jun 13, 1989E. I. Du Pont De Nemours And CompanyPolyimide gas separation membranes
US4851505 *Apr 13, 1988Jul 25, 1989E. I. Du Pont De Nemours And CompanyHighly soluble aromatic polyimides
US4880442 *Dec 22, 1987Nov 14, 1989E. I. Du Pont De Nemours And CompanyPolyimide gas separation membranes
US4925912 *Dec 8, 1988May 15, 1990Ciba-Geigy CorporationAuto-photocrosslinkable copolyimides and polyimide compositions
US4935320 *Aug 12, 1988Jun 19, 1990Ciba-Geigy CorporationAdhesively bonded photostructurable polyimide film
US4935490 *Apr 13, 1988Jun 19, 1990E. I. Dupont De Nemours And CompanyHighly soluble aromatic polyimides
US5326792 *Nov 23, 1992Jul 5, 1994Chisso CorporationPolyimide photosensitive cover coating agent
US5464927 *May 10, 1993Nov 7, 1995International Business Machines CorporationPolyamic acid and polyimide from fluorinated reactant
US5780199 *May 16, 1995Jul 14, 1998International Business Machines CorporationPolyamic acid and polyimide from fluorinated reactant
US6379865Apr 11, 2000Apr 30, 20023M Innovative Properties CompanyPhotoimageable, aqueous acid soluble polyimide polymers
US6559245Jan 3, 2002May 6, 20033M Innovative Properties CompanyPhotoimageable, aqueous acid soluble polyimide polymers
US6803092Jun 26, 2001Oct 12, 20043M Innovative Properties CompanySelective deposition of circuit-protective polymers
US20030175272 *Mar 7, 2002Sep 18, 2003Medcell Biologics, Inc.Re-activated T-cells for adoptive immunotherapy
US20030180664 *Mar 18, 2003Sep 25, 20033M Innovative Properties CompanyPhotoimageable, aqueous acid soluble polyimide polymers
US20030211425 *Mar 18, 2003Nov 13, 20033M Innovative Properties CompanyPhotoimageable, aqueous acid soluble polyimide polymers
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Classifications
U.S. Classification430/583, 528/229, 522/164, 430/270.1, 528/331, 528/329.1, 528/220, 522/162
International ClassificationC07C229/62, C07C227/00, C09D179/08, C08G73/10, C08G73/00, C07C67/00, G03F7/038
Cooperative ClassificationY10T428/31721, Y10S430/107, C08G73/1067, C08G73/1085, C08G73/1003, C08G73/1057, C08G73/1082, G03F7/0387
European ClassificationC08G73/10M, C08G73/10B, C08G73/10Q, G03F7/038P, C08G73/10N, C08G73/10P2
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